Dark NO Reduction on a Graphene Surface with Implications for Soot Aging and HONO Formation.

Soot, primarily composed of elemental carbon (EC) and organic carbon (OC), is ubiquitous in PM. In the atmosphere, the heterogeneous interaction between NO and soot is not only an important pathway driving soot aging but also of central importance to nitrous acid (HONO) formation. It is commonly believed that the surface redox reaction between reductive OC and NO dominates the night aging of soot and the conversion of NO to HONO. However, completely differing from the currently popular explanation, we find here that the redox reaction between EC and NO can also drive the conversion of NO to HONO during soot aging. By combining in situ experiments with density functional theory (DFT) calculations, we proposed that the surface carbon vacancy defects on graphite/graphene-like EC should be a type of potential primary adsorption and reactive sites inducing the heterogeneous reduction of NO. We suggested a new mechanism that NO is reduced to form HONO on surface vacancy defects through the splitting of HO molecules, and the carbon atoms adjacent to surface vacancy are simultaneously oxidized to form hydroxyl-functionalized EC. This novel finding provides insights into the chemical mechanism driving the NO-to-HONO conversion and rapid soot aging, which expands our knowledge of the heterogeneous chemistry of soot in the atmosphere.